N-acyl proline derivatives as food flavoring compounds

ABSTRACT

A flavour composition comprising a compound of formula (I) corresponding to the formula 
     
       
         
         
             
             
         
       
         
         and edible salts thereof, 
         wherein 
         R 1  is an alkyl residue containing 6 to 20 carbon atoms, or an alkene residue containing from 9 to 25 carbon atoms with 1 to 6 double bonds, R 1  together with the carbonyl group to which it is attached is a residue of a carboxylic acid.

This is an application filed under 35 USC 371 of PCT/US2013/034378,which in turn claims priority to U.S. 61/617,796 filed 30 Mar. 2012.

The invention is concerned with certain carboxylic acid-amino acidconjugates, flavour compositions containing said conjugates, and theiruse in edible compositions.

Many food flavour ingredients are known in the art that exert their ownvery pronounced flavour characteristics to a food product. Suchingredients may be of great value in niche areas for particular types offood categories, but can be incongruous, or even offensive, whenemployed in other food categories.

There is a need to provide broad spectrum flavour ingredients that actto complement or accentuate the taste and mouthfeel characteristics ofthe edible compositions into which they are incorporated.

The applicant has now found a group of compounds that may be employedflavour ingredients that complement or accentuate the taste andmouthfeel characteristics of edible compositions into which they areincorporated across a wide category of flavour applications.

The present invention provides in a first aspect compounds of formula(I) corresponding to the formula

their edible salts, and their use in edible compositions

wherein

R₁ is an alkyl residue containing 6 to 20 carbon atoms, or an alkeneresidue containing from 9 to 25 carbon atoms with 1 to 6 double bonds,R₁ together with the carbonyl group to which it is attached is a residueof a carboxylic acid.

Edible salts include those typically employed in the food and beverageindustry and include chlorides, sulphates, phosphates, gluconates,sodium, citrates, carbonates, acetates and lactates.

The skilled person will appreciate that the amino acid residue in thecompounds defined above is the proline residue (Pro).

Henceforth, when referring to the amino acid or its residue, use may bemade of the three letter abbreviation used above in parentheses.

The carboxylic acids can likewise be represented by abbreviations.Henceforth, the carboxylic acid residues may be referred to by theabbreviation Cn, wherein “n” represents the number of carbon atoms inthe residue. For example, the residue of an 18 carbon acid may beabbreviated as C18. Still further, if the 18 carbon acid is saturated,e.g. stearic acid. It may be abbreviated as C18:0 (because it containszero double bonds), whereas an 18 carbon acid having one doublebond—e.g. oleic acid—may be abbreviated as C18:1. Still further, if theC18 acid has a single double bond in the cis configuration, then it canbe abbreviated as C18:1c. Similarly, if the double bond was in the transconfiguration, then the abbreviation becomes C18:1t.

In a particular embodiment of the present invention the carboxylic acidresidue is a residue of a fatty acid.

The fatty acid residue may be the residue of a C8 to C22 fatty acid. Thefatty acid may be mammalian or non-mammalian. A mammalian fatty acid isa natural or synthetic fatty acid that is identical in structure to onenaturally produced in a mammal, including, but not limited to, myristicacid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenicacid, eicosatrienoic acid, arachidonic acid, eicosapentenoic acid, anddocosatetraenoic acid. A non-mammalian fatty acid is a natural orsynthetic fatty acid not normally produced by a mammal, including, butnot limited to, pentadecanoic acid; heptadecanoic acid; nonadecanoicacid; heneicosanoic acid; 9-trans-tetradecenoic acid;10-trans-pentadecenoic acid; 9-trans-hexadecenoic acid;10-trans-heptadecenoic acid; 10-trans-heptadecenoic acid;7-trans-nonadecenoic acid; 10,13-nonadecadienoic acid;11-trans-eicosenoic acid; and 12-transhenicosenoic acid.

The fatty acid residues may be saturated or unsaturated. If they areunsaturated, it is preferred that they have 1, 2 or 3 double bonds,which may in cis- or trans-configuration. More particularly, thepreferred fatty acid residues are C16 to C18, and may be saturated orunsaturated.

The skilled person will appreciate, however, that natural sources ofthese fatty acids, for example almond oil, avocado oil, castor oil,coconut oil, corn oil, cottonseed oil, olive oil, peanut oil, rice branoil, safflower oil, sesame oil, soybean oil, sunflower oil, palm oil andcanola oil, each consist of a complex mixture of fatty acids. Forexample, safflower oil is predominately a source of the C18:2 linoleicacid, nevertheless it may contain other fatty acids, such as linolenicacid (C18:3) and palmitic acid (C16:0), amongst others. Accordingly,reference herein to a compound containing a particular fatty acidresidue, for example a residue of C18 fatty acid, may be a reference toa pure, or substantially pure C18 fatty acid residue, or it may relateto a mixture of fatty acid residues with the predominant residue being aC18 residue. Preferred fatty acid residues are C16 to C18.

The compounds of formula (I) can also be represented using theseabbreviations. For example, the compound of formula (I) consisting of aresidue of a C18 carboxylic acid and a residue of the amino acid Proline(Pro) can be represented by the abbreviation C18-Pro. For simplicity thecompounds of formula (I) henceforth may be represented in thisabbreviated form.

As is evident from the above formula (I), the amino nitrogen atom on theamino acid residue is bound to a carbonyl carbon atom of the carboxylicacid residue to form an amide linkage. Thus, the abbreviated formC18-Pro represents the compound of formula (I) in which the residue ofProline is connected via its nitrogen atom to the carbonyl carbon atomof a C18 carboxylic acid.

These compounds are particularly effective to enhance juiciness andtypical citrus authenticity. They find use particularly in powdered softdrinks and beverages, and also in dairy applications, such as fruitflavoured milk, yoghurt and ice creams.

The compounds include C8-Pro, C9-Pro, C10-Pro, C12-Pro, C14-Pro,C16-Pro, C18-Pro, C20-Pro and C22-Pro.

The compounds include C8-Pro, C9-Pro, C10-Pro, C12-Pro, C14-Pro,C16-Pro, C18-Pro, C20-Pro and C22-Pro, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Pro, C9-Pro, C10-Pro, C12-Pro, C14-Pro,C16-Pro, C18-Pro, C20-Pro and C22-Pro, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Pro residue N-geranoyl-Pro,N-palmitoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-linoleoyl-Pro andN-linolenoyl-Pro.

The compounds of formula (I) can be formed by known methods usingcommercially available starting materials, reagents and solvents, and adetailed discussion is not warranted here. In an embodiment of thepresent invention, the conjugates can be formed by the reaction of anamino acid with a fatty acid halide, e.g. a chloride under basicconditions in aqueous conditions such as a water/THF solvent system.Yield and reaction times may be improved by applying heat to thereaction mixture. In an alternative embodiment, a fatty acid can bereacted with an amino acid in dioxane in the presence of DCC(dicyclohexylcarbodiimide) and 1-hydroxypyrrolidine-2,5-dione.

In yet another embodiment, an amino acid alkyl ester may be reacted witha fatty acid chloride under basic conditions in an aqueous-basedsolvent, such as a water/THF solvent system. Thereafter, the ester canbe hydrolysed carefully without affecting the amide bond in basicmethanol water solution

In yet another embodiment, a fatty acid and an amino acid alkyl estercan be reacted in dioxane in the presence of DCC(dicyclohexylcarbodiimide) and 1-hydroxypyrrolidine-2,5-dione. The estercan be hydrolysed carefully without affecting the amide bond in dilutebasic methanol water solution

In yet another embodiment, a (mixed) anhydride of a fatty acid isreacted with an amino acid in dioxane.

In yet another embodiment, a fatty acid alkyl ester can be reacted withan amino acid in dioxane

In still another embodiment, an amino acid alkyl ester is reacted with atriglyceride, optionally in the presence of a co-solvent. The amino acidester thus formed is then hydrolysed according to a method describedabove.

In yet another embodiment, an amino acid is reacted with a triglyceride,optionally in the presence of a co-solvent.

In yet another embodiment, an amino acid is reacted with a triglyceridein the presence of a lipase, esterase, peptidase, amidase or acylase,optionally in the presence of a cosolvent and/or water.

In yet another embodiment a fatty acid alkyl ester is reacted with anamino acid in the presence of a lipase or an acylase, optionally in thepresence of a co-solvent and/or water.

The compounds of formula (I) impart remarkable organoleptic propertiesto edible compositions to which they are added. In particular, theyimpart highly intense, authentic and harmonious flavour, and a roundnessand fullness to edible compositions containing them.

More particularly, the compounds can be incorporated into an edibleproduct to impart a remarkable mouthfeel, body and enhanced fatperception; or an enhanced umami or salt taste; or a cooling andrichness. They are particularly useful in applications low in fat, saltand umami. They are also useful in fat-free formulations such asbeverages and oral care applications. They also find use in dairyapplications and in vanilla, cocoa and chocolate

This finding was all the more surprising considering that when applicanttasted the compounds in dilute aqueous solution, they were eithertasteless or they exhibited a disappointing, faintly fatty tasteprofile. As such, they appeared to be quite unsuitable for use inflavour applications. Only their combination with flavour co-ingredientsand the judicious selection of their usage levels was it possible todiscover the remarkable organoleptic properties of these compounds.Their effect on edible compositions is quite unusual in that rather thanexerting a characteristic flavour profile to a foodstuff or a beverage,they actually complement, lift or accentuate the essential or authenticflavour and mouth feel characteristics of the foods or beverages inwhich they are incorporated. Accordingly, the compounds of the presentinvention find utility in a broad spectrum of applications in the foodand beverage industry, as well as in health and wellness.

Accordingly, the invention provides in another of its aspects, a methodof conferring flavour and/or mouthfeel to, or improving taste and/ormouthfeel of an edible composition, which method comprises adding tosaid composition a compound of formula (I) defined herein.

The remarkable organoleptic effects are observed when the compounds offormula (I) are incorporated into an edible composition containing oneor more flavour co-ingredients.

The flavour co-ingredients may be sugars, fats, salt (e.g. sodiumchloride), MSG, calcium ions, phosphate ions, organic acids, proteins,purines and mixtures thereof.

In a particular embodiment, sugars are present in amounts of 0.001% to90%, more particularly 0.001% to 50%, still more particularly 0.001% to20% based on the total weight of an edible composition.

In a particular embodiment, fats are present in amounts of 0.001% to100%, more particularly 0.001% to 80%, more particularly 0.001% to 30%,still more particularly 0.001% to 5% based on the total weight of anedible composition.

In a particular embodiment, salt (e.g. sodium chloride) is present inamounts of 0.001% to 20%, more particularly 0.001% to 5% based on thetotal weight of an edible composition.

In a particular embodiment, MSG is present in amounts of 0.001% to 2%based on the total weight of an edible composition.

In a particular embodiment, calcium is present in amounts of 0.001% to50% more particularly 0.001% to 20%, still more particularly 0.001% to1% based on the total weight of an edible composition.

In a particular embodiment, organic acids are present in amounts of0.001% to 10%, more particularly 0.001% to 7% based on the total weightof an edible composition.

Types of organic acids include citric, malic, tartaric, fumaric, lactic,acetic, succinic. Types of edible compositions containing organic acidsinclude beverages, such as carbonated soft drink beverages, stillbeverages, Juices, powdered soft drinks, liquid concentrates, alcoholicbeverages and functional beverages.

In a particular embodiment, phosphorus is present in an amount up to0.5% by weight of an edible composition. Typically phosphorus is presentas a phosphate or phosphoric acid.

In a particular embodiment, purines are present in an amount up to 0.5%by weight of an edible composition. The term “purines” includeribonucleotides such as IMP and GMP.

Despite their interesting organoleptic properties, nevertheless,applicant found that formulating the compounds of formula (I) was not atrivial matter. The discovered potency of the compounds suggested thatthey could be employed at very low levels in flavour applications, andso for ease of handling, mixing and processing with other ingredients,although it is possible to use the compounds in neat form, it isdesirable to extend or add volume to the physical form of the compoundsby incorporating them into a suitable vehicle, for example a diluent,such as a solvent. However, the compounds are solids or viscous oils atambient temperatures, and have very limited solubility in water.Applicant found that an at least about 0.01% stock solution, moreparticularly about 0.01-1% stock solution of a compound of formula (I)achieved a balance regarding acceptable solvent levels for ease ofhandling and mixing, and the desire to limit the amount of solvent thatwould have to be removed from the stock solution when further processingof the compounds in flavour compositions and edible products for reasonsof palatability, efficiency, cost and the like. Applicant found thatsuitable solvents for the stock solution include ethanol, triacetine,glycerol and miglyol.

In order to aid in the process of solubilization and produce a stocksolution and minimize the amount of solvent, it is preferred to usecompounds of the formula (I) formed from a mixture of carboxylic acids,rather than a pure carboxylic acid.

Accordingly, the invention provides in another of its aspects an atleast about 0.01% stock solution, more particularly about 0.01-1% stocksolution of a compound of formula (I).

The stock solution may contain other materials such as carrier materialsand/or adjuvants more fully described below. In a particular embodiment,the stock solution contains an anti-oxidant selected from the groupconsisting of vitamin C, vitamin E, rosemary extract, antrancine,butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT).Anti-oxidants are preferably employed to prevent, or significantlyreduce, generation of volatile off notes as a result of degradation ofthe compounds of formula (I). Anti-oxidants are particularly preferredwhen the compounds of formula (I) bear a residue of an unsaturated fattyacid. Anti-oxidants are particularly preferred if the fatty acid residuecontains more than 1 double bond. Determination of an effective amountof anti-oxidant is within the purview of the skilled person, howeveramounts in the range of about 10 ppm to 1000 ppm based on the weight ofthe stock solution may be present.

In preparing the flavour compositions of the present invention, thecompounds of formula (I) may be employed in any physical form. They maybe used in neat form, in the form of a stock solution described above;they may be used in the form of an emulsion; or they may be used in apowder form. If the compounds of formula (I) are presented in the formof a powder, the powder form can be produced by a dispersive evaporationprocess, such as a spray drying process as is more fully describedbelow. The powder form may be prepared by subjecting a liquidformulation containing a compound of formula (I) to a dispersiveevaporation process. The liquid formulation may comprise a solution,suspension or emulsion comprising the compound of formula (I). Inparticular, the liquid formulation may take the form of the stocksolution described hereinabove. The liquid formulation may contain otheringredients such as a carrier material and/or an adjuvant as describedmore fully below.

A powder comprising a compound of formula (I) forms another aspect ofthe present invention.

The compounds of formula (I) may in incorporated into an ediblecomposition alone, or in the form of a flavour composition comprisingone or more flavour co-ingredients.

A flavour composition comprising a compound according to the formula (I)forms another aspect of the present invention.

In an embodiment of the present invention, the flavour formulationcomprises a compound of formula (I) and at least flavour co-ingredient.

In a particular embodiment of the present invention the flavourcomposition comprises:

-   -   i) a compound according to formula (I);    -   ii) at least one flavour co-ingredient;    -   iii) optionally a carrier material; and    -   iv) optionally at least one adjuvant.

By the term “flavour co-ingredient” is an ingredient that is able tocontribute or impart or modify in a positive or pleasant way the tasteof an edible composition.

All manner of flavour co-ingredients may be employed in a compositionaccording to the present invention, including, but not limited tonatural flavours, artificial flavours, spices, seasonings, and the like.Flavour co-ingredients include synthetic flavour oils and flavouringaromatics and/or oils, oleoresins, essences, distillates, and extractsderived from plants, leaves, flowers, fruits, and so forth, andcombinations comprising at least one of the foregoing.

Flavour oils include spearmint oil, cinnamon oil, oil of wintergreen(methyl salicylate), peppermint oil, Japanese mint oil, clove oil, bayoil, anise oil, eucalyptus oil, thyme oil, cedar leaf oil, oil ofnutmeg, allspice, oil of sage, mace, oil of bitter almonds, and cassiaoil; useful flavouring agents include artificial, natural and syntheticfruit flavours such as vanilla, and citrus oils including lemon, orange,lime, grapefruit, yazu, sudachi, and fruit essences including apple,pear, peach, grape, blueberry, strawberry, raspberry, cherry, plum,prune, raisin, cola, guarana, neroli, pineapple, apricot, banana, melon,apricot, ume, cherry, raspberry, blackberry, tropical fruit, mango,mangosteen, pomegranate, papaya and the like.

Additional exemplary flavours imparted by a flavouring agent include amilk flavour, a butter flavour, a cheese flavour, a cream flavour, and ayogurt flavour; a vanilla flavour; tea or coffee flavours, such as agreen tea flavour, an oolong tea flavour, a tea flavour, a cocoaflavour, a chocolate flavour, and a coffee flavour; mint flavours, suchas a peppermint flavour, a spearmint flavour, and a Japanese mintflavour; spicy flavours, such as an asafetida flavour, an ajowanflavour, an anise flavour, an angelica flavour, a fennel flavour, anallspice flavour, a cinnamon flavour, a chamomile flavour, a mustardflavour, a cardamom flavour, a caraway flavour, a cumin flavour, a cloveflavour, a pepper flavour, a coriander flavour, a sassafras flavour, asavoury flavour, a Zanthoxyli Fructus flavour, a perilla flavour, ajuniper berry flavour, a ginger flavour, a star anise flavour, ahorseradish flavour, a thyme flavour, a tarragon flavour, a dillflavour, a capsicum flavour, a nutmeg flavour, a basil flavour, amarjoram flavour, a rosemary flavour, a bayleaf flavour, and a wasabi(Japanese horseradish) flavour; a nut flavour such as an almond flavour,a hazelnut flavour, a macadamia nut flavour, a peanut flavour, a pecanflavour, a pistachio flavour, and a walnut flavour; alcoholic flavours,such as a wine flavour, a whisky flavour, a brandy flavour, a rumflavour, a gin flavour, and a liqueur flavour; floral flavours; andvegetable flavours, such as an onion flavour, a garlic flavour, acabbage flavour, a carrot flavour, a celery flavour, mushroom flavour,and a tomato flavour.

In some embodiments, said flavour co-ingredients include aldehydes andesters such as cinnamyl acetate, cinnamaldehyde, citral diethylacetal,dihydrocarvyl acetate, eugenyl 49 formate, p-methylamisol, and so forthcan be used. Further examples of aldehyde flavourings includeacetaldehyde (apple), benzaldehyde (cherry, almond), anisic aldehyde(licorice, anise), cinnamic aldehyde (cinnamon), citral, i.e.,alpha-citral (lemon, lime), neral, i.e., beta-citral (lemon, lime),decanal (orange, lemon), ethyl vanillin (vanilla, cream), heliotrope,i.e., piperonal (vanilla, cream), vanillin (vanilla, cream), alpha-amylcinnamaldehyde (spicy fruity flavours), butyraldehyde (butter, cheese),valeraldehyde (butter, cheese), citronellal (modifies, many types),decanal (citrus fruits), aldehyde C-8 (citrus fruits), aldehyde C-9(citrus fruits), aldehyde C-12 (citrus fruits), 2-ethyl butyraldehyde(berry fruits), hexenal, i.e., trans-2 (berry fruits), tolyl aldehyde(cherry, almond), veratraldehyde (vanilla), 2,6-dimethyl-5-heptenal,i.e., melonal (melon), 2,6-dimethyloctanal (green fruit), and2-dodecenal (citrus, mandarin), and the like.

Further examples of other flavour co-ingredients can be found in“Chemicals Used in Food Processing”, publication 1274, pages 63-258, bythe National Academy of Sciences.

Flavour co-ingredients can also include salt tastants, umami tastants,and savoury flavour compounds. Non limiting examples include: NaCl, KCl,MSG, guanosine monophosphate (GMP), inosin monophospahte (IMP),ribonucleotides such as disodium inosinate, disodium guanylate,N-(2-hydroxyethyl)-lactamide, N-lactoyl-GMP, N-lactoyl tyramine, gammaamino butyric acid, allyl cysteine,1-(2-hydroxy-4-methoxylphenyl)-3-(pyridine-2-yl)propan-1-one, arginine,potassium chloride, ammonium chloride, succinic acid,N-(2-methoxy-4-methyl benzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(heptan-4-yl)benzo(D)(1,3)dioxole-5-carboxamide,N-(2,4-dimethoxybenzyl)-N′-(2-(pyridin-2-yl)ethyl)oxalamide,N-(2-methoxy-4-methylbenzyl)-N′-2(2-(5-methylpyridin-2-yl)ethyl)oxalamide,cyclopropyl-E,Z-2,6-nonadienamide.

In particular embodiments of the present invention, the flavourco-ingredient is selected from the compounds and compositions disclosedin WO2005102701, WO2006009425, WO2005096843, WO2006046853 andWO2005096844, all of which references are herein incorporated byreference in their entirety.

Flavour co-ingredients may include known salt tastants, umami tastants,and savoury flavour compounds. Non limiting examples include: NaCl, KCl,MSG, guanosine monophosphate (GMP), inosin monophospahte (IMP),ribonucleotides such as disodium inosinate, disodium guanylate,N-(2-hydroxyethyl)-lactamide, N-lactoyl-GMP, N-lactoyl tyramine, gammaamino butyric acid, allyl cysteine,1-(2-hydroxy-4-methoxylphenyl)-3-(pyridine-2-yl)propan-1-one, arginine,potassium chloride, ammonium chloride, succinic acid,N-(2-methoxy-4-methyl benzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(heptan-4-yl)benzo(D)(1,3)dioxole-5-carboxamide,N-(2,4-dimethoxybenzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(2-methoxy-4-methyl benzyl)-N′-2(2-(5-methylpyridin-2-yl)ethyl)oxalamide, cyclopropyl-E,Z-2,6-nonadienamide.

The carrier material may be employed in compositions according to theinvention to encapsulate or to entrap in a matrix the other componentsof the composition. The role of the carrier material may be merely thatof a processing aid or a bulking agent, or it might be employed toshield or protect the other components from the effects of moisture oroxygen or any other aggressive media. The carrier material might alsoact as a means of controlling the release of flavour from ediblecompositions.

Carrier materials may include mono, di- or trisaccharides, natural ormodified starches, hydrocolloids, cellulose derivatives, polyvinylacetates, polyvinylalcohols, proteins or pectins. Example of particularcarrier materials include sucrose, glucose, lactose, levulose, fructose,maltose, ribose, dextrose, isomalt, sorbitol, mannitol, xylitol,lactitol, maltitol, pentatol, arabinose, pentose, xylose, galactose,maltodextrin, dextrin, chemically modified starch, hydrogenated starchhydrolysate, succinylated or hydrolysed starch, agar, carrageenan, gumarabic, gum accacia, tragacanth, alginates, methyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethylcellulose, derivatives and mixtures thereof. Of course, the skilledaddresse with appreciate that the cited materials are hereby given byway of example and are not to be interpreted as limiting the invention.

By “flavour adjuvant” is meant an ingredient capable of impartingadditional added benefit to compositions of the present invention suchas a colour, light resistance, chemical stability and the like. Suitableadjuvants include solvents (including water, alcohol, ethanol,triacetine, oils, fats, vegetable oil and miglyol), binders, diluents,disintegrating agents, lubricants, colouring agents, preservatives,antioxidants, emulsifiers, stabilisers, anti-caking agents, and thelike. In a particular embodiment, the flavour composition comprises ananti-oxidant. Said anti-oxidants may include vitamin C, vitamin E,rosemary extract, antrancine, butylated hydroxyanisole (BHA) andbutylated hydroxytoluene (BHT).

Examples of such carriers or adjuvants for flavour compositions may befound in for example, “Perfume and Flavour Materials of Natural Origin”,S. Arctander, Ed., Elizabeth, N.J., 1960; in “Perfume and FlavourChemicals”, S. Arctander, Ed., Vol. I & II, Allured PublishingCorporation, Carol Stream, USA, 1994; in “Flavourings”, E. Ziegler andH. Ziegler (ed.), Wiley-VCH Weinheim, 1998, and “CTFA CosmeticIngredient Handbook”, J. M. Nikitakis (ed.), 1st ed., The Cosmetic,Toiletry and Fragrance Association, Inc., Washington, 1988.

Other suitable and desirable ingredients of flavour compositions aredescribed in standard texts, such as “Handbook of Industrial ChemicalAdditives”, ed. M. and I. Ash, 2^(nd) Ed., (Synapse 2000).

Flavour compositions according to the present invention may be providedin any suitable physical form. For example, they may be in the form ofoils, emulsions or dispersions in a hydrous liquid or organic liquidsuitable for use in edible compositions, or solid form, such as powders.

If the flavour compositions are to be provided in the form of a powderedcomposition, they may be prepared by dispersive evaporation techniquesgenerally known in the art, such as spray drying.

Accordingly, in another aspect of the present invention there isprovided a method of forming a powder composition, comprising the stepsof providing a liquid composition comprising a compound of the formula(I) and one or more optional ingredients selected from at least oneflavour co-ingredient, a carrier material and an adjuvant, anddispersively evaporating said liquid composition to form a powdercomposition.

In this manner, a compound of formula (I) or a flavour compositioncomprising said compound may be presented in a powder form.

The liquid composition used in the preparation of a powder may be in theform of a solution, emulsion, dispersion or slurry. The liquid maycontain water, and/or an organic liquid, such as ethanol, glycerol,triacetine, miglyol (MCT) that is acceptable for use in ediblecompositions.

Powder compositions according to the present invention may be preparedaccording to methods and apparatus known in the art for producingpowders on an industrial scale. A particularly suitable method is spraydrying. Spray drying techniques and apparatus are well known in the artand need no detailed discussion herein. The spray drying techniques,apparatus and methods described in US2005/0031769 and US2013/0022728, aswell as those techniques, apparatus and methods described in thosedocuments are suitable for producing powder compositions of the presentinvention and are herein incorporated by reference in their entirety.

The manner in which the compounds of formula (I) are incorporated intopowder flavour compositions of the invention is not critical. Forexample, the compounds may be added to the liquid composition describedabove and be subjected to a dispersive evaporation process along withall the other components of the flavour composition. Alternatively,compounds may be added to the flavour composition after it has beenformed as a powder.

Many of the flavour co-ingredients described herein above are volatileand/or may be sensitive to oxidative degradation, particularly whensubjected to elevated temperature, and under humid conditions.Accordingly, particular problems can arise when subjecting flavourco-ingredients described above to dispersive evaporation processes suchas spray drying. A non-exhaustive list of ingredients that can beparticularly susceptible include, those ingredients containingartificial, natural or synthetic fruit flavours such as vanilla,chocolate, coffee, cocoa and citrus oil, including lemon, orange, grape,lime and grapefruit, and fruit essences including apple, pear, peach,strawberry, raspberry, cherry, plum, pineapple, apricot and the like.The volatile components of these flavour co-ingredients may include, butare not limited to, acetaldehyde, dimethyl sulfide, ethyl acetate, ethylpropionate, methyl butyrate, and ethyl butyrate. Flavour co-ingredientscontaining volatile aldehydes or esters include, e.g., cinnamyl acetate,cinnamaldehyde, citral, diethylacetal, dihydrocarvyl acetate, eugenylformate, and p-methylanisole. Further examples of volatile compoundsthat may be present as co-ingredients include acetaldehyde (apple);benzaldehyde (cherry, almond); cinnamic aldehyde (cinnamon); citral,i.e., alpha citral (lemon, lime); neral, i.e., beta citral (lemon,lime); decanal (orange, lemon); ethyl vanillin (vanilla, cream);heliotropine, i.e., piperonal (vanilla, cream); vanillin (vanilla,cream); alpha-amyl cinnamaldehyde (spicy fruity flavors); butyraldehyde(butter, cheese); valeraldehyde (butter, cheese); citronellal (modifies,many types); decanal (citrus fruits); aldehyde C-8 (citrus fruits);aldehyde C-9 (citrus fruits); aldehyde C-12 (citrus fruits); 2-ethylbutyraldehyde (berry fruits); hexenal, i.e., trans-2 (berry fruits);tolyl aldehyde (cherry, almond); veratraldehyde (vanilla);2,6-dimethyl-5-heptenal, i.e., melonal (melon); 2-6-dimethyloctanal(green fruit); and 2-dodecenal (citrus, mandarin); cherry; or grape andmixtures thereof.

Applicant surprisingly found that the inclusion of a compound of formula(I) in a powder flavour composition, it was possible to maintain theflavour quality of flavour composition converted into powdered form by adispersive evaporation process.

Accordingly, the invention provides in another of its aspects a methodof maintaining flavour quality of a powder flavour compositioncomprising the step of including in said powder flavour composition acompound of formula (I)

As stated hereinabove, compounds of formula (I) or flavour compositionscontaining such compounds can be incorporated into edible compostions,and an edible composition containing such a compound or flavourcomposition forms another aspect of the present invention.

The term “edible composition” refers to products for consumption by asubject, typically via the oral cavity (although consumption may occurvia non-oral means such as inhalation), for at least one of the purposesof enjoyment, nourishment, or health and wellness benefits. Ediblecompositions may be present in any form including, but not limited to,liquids, solids, semi-solids, tablets, capsules, lozenges, strips,powders, gels, gums, pastes, slurries, syrups, aerosols and sprays. Theterm also refers to, for example, dietary and nutritional supplements.Edible compositions include compositions that are placed within the oralcavity for a period of time before being discarded but not swallowed. Itmay be placed in the mouth before being consumed, or it may be held inthe mouth for a period of time before being discarded. An ediblecomposition as herein above defined includes compositions whose taste ismodified in the manner described herein by the addition of compounds offormula (I) or whose taste is so modified by processing such that it isenriched in a compound of formula (I).

In a particular embodiment the term “edible compositions” refers toproducts for consumption by a subject, typically via the oral cavity(although consumption may occur via non-oral means such as inhalation),for one of the purposes of enjoyment or nourishment.

In a more particular embodiment the term “edible compositions” refers toproducts for consumption by a subject, typically via the oral cavity(although consumption may occur via non-oral means such as inhalation),for the purpose of enjoyment. Still more particularly, the term refersto foodstuffs and beverages.

In a particular embodiment, the term “edible composition” does notrelate to pharmaceutical compositions.

In another embodiment, the term “edible composition” does not relate tonutritional supplements.

Broadly, the edible composition includes, but is not limited tofoodstuffs of all kinds, confectionery products, baked products, sweetproducts, savoury products, fermented products, dairy products,beverages and oral care products.

Exemplary foodstuffs include, but are not limited to, chilled snacks,sweet and savoury snacks, fruit snacks, chips/crisps, extruded snacks,tortilla/corn chips, popcorn, pretzels, nuts, other sweet and savourysnacks, snack bars, granola bars, breakfast bars, energy bars, fruitbars, other snack bars, meal replacement products, slimming products,convalescence drinks, ready meals, canned ready meals, frozen readymeals, dried ready meals, chilled ready meals, dinner mixes, frozenpizza, chilled pizza, soup, canned soup, dehydrated soup, instant soup,chilled soup, uht soup, frozen soup, pasta, canned pasta, dried pasta,chilled/fresh pasta, noodles, plain noodles, instant noodles, cups/bowlinstant noodles, pouch instant noodles, chilled noodles, snack noodles,dried food, dessert mixes, sauces, dressings and condiments, herbs andspices, spreads, jams and preserves, honey, chocolate spreads, nut-basedspreads, and yeast-based spreads.

Exemplary confectionery products include, but are not limited to,chewing gum (which includes sugarized gum, sugar-free gum, functionalgum and bubble gum), centerfill confections, chocolate and otherchocolate confectionery, medicated confectionery, lozenges, tablets,pastilles, mints, standard mints, power mints, chewy candies, hardcandies, boiled candies, breath and other oral care films or strips,candy canes, lollipops, gummies, jellies, fudge, caramel, hard and softpanned goods, toffee, taffy, liquorice, gelatin candies, gum drops,jelly beans, nougats, fondants, combinations of one or more of theabove, and edible flavour compositions incorporating one or more of theabove.

Exemplary baked products include, but are not limited to, alfajores,bread, packaged/industrial bread, unpackaged/artisanal bread, pastries,cakes, packaged/industrial cakes, unpackaged/artisanal cakes, cookies,chocolate coated biscuits, sandwich biscuits, filled biscuits, savourybiscuits and crackers, bread substitutes,

Exemplary sweet products include, but are not limited to, breakfastcereals, ready-to-eat (“rte”) cereals, family breakfast cereals, flakes,muesli, other ready to eat cereals, children's breakfast cereals, hotcereals,

Exemplary savoury products include, but are not limited to, salty snacks(potato chips, crisps, nuts, tortilla-tostada, pretzels, cheese snacks,corn snacks, potato-snacks, ready-to-eat popcorn, microwaveable popcorn,pork rinds, nuts, crackers, cracker snacks, breakfast cereals, meats,aspic, cured meats (ham, bacon), luncheon/breakfast meats (hotdogs, coldcuts, sausage), tomato products, margarine, peanut butter, soup (clear,canned, cream, instant, UHT), canned vegetables, pasta sauces.

Exemplary dairy products include, but are not limited to, cheese, cheesesauces, cheese-based products, ice cream, impulse ice cream, singleportion dairy ice cream, single portion water ice cream, multi-packdairy ice cream, multi-pack water ice cream, take-home ice cream,take-home dairy ice cream, ice cream desserts, bulk ice cream, take-homewater ice cream, frozen yoghurt, artisanal ice cream, dairy products,milk, fresh/pasteurized milk, full fat fresh/pasteurized milk, semiskimmed fresh/pasteurized milk, long-life/uht milk, full fat longlife/uht milk, semi skimmed long life/uht milk, fat-free long life/uhtmilk, goat milk, condensed/evaporated milk, plain condensed/evaporatedmilk, flavoured, functional and other condensed milk, flavoured milkdrinks, dairy only flavoured milk drinks, flavoured milk drinks withfruit juice, soy milk, sour milk drinks, fermented dairy drinks, coffeewhiteners, powder milk, flavoured powder milk drinks, cream, yoghurt,plain/natural yoghurt, flavoured yoghurt, fruited yoghurt, probioticyoghurt, drinking yoghurt, regular drinking yoghurt, probiotic drinkingyoghurt, chilled and shelf-stable desserts, dairy-based desserts,soy-based desserts.

Exemplary beverages include, but are not limited to, flavoured water,soft drinks, fruit drinks, coffee-based drinks, tea-based drinks,juice-based drinks (includes fruit and vegetable), milk-based drinks,gel drinks, carbonated or non-carbonated drinks, powdered drinks,alcoholic or non-alcoholic drinks.

Exemplary fermented foods include, but are not limited to, Cheese andcheese products, meat and meat products, soy and soy products, fish andfish products, grain and grain products, fruit and fruit products.

In a particular embodiment the consumable product is selected from thegroup consisting of soy sauce, cheese, soup, hot and cold sauces,fruits, vegetables, ketchups, tea, coffee, snacks such as potato chipsor extruded snacks.

The compounds of formula (I), when added to a flavour composition and/oran edible composition act on the composition to complement its flavourand/or mouthfeel to render it more delicious and authentic. The effectsmay be temporal or related to intensity, for example the compounds mayact by enhancing, strengthening, softening, sharpening a flavour, ormaking more salivating. The compounds of formula (I) may also affect thetemporal profile of a flavour, that is, they may affect the initialimpact of a flavour, the body of a flavour, or its lingering effect.

The compounds of formula (I) may modify any aspect of the temporalprofile of taste or flavour of an edible composition. In particular, thecompounds improve mouthfeel and impart more creamy and fatty sensations.

Compounds of formula (I) or flavour compositions containing same may beadded to edible compositions in widely carrying amounts. The amount willdepend on the nature of the edible composition to be flavoured, and onthe desired effect, as well as on the nature of the ingredients presentin said flavour composition. In order to obtain the remarkablebeneficial effects attributed to the presence of the compounds offormula (I), the flavour composition should be employed in amounts suchthat the compounds of formula (I) are present in amounts of 1 part perbillion to 10 parts per million based on the total weight of the ediblecomposition. Whereas amounts higher than this can be employed, thebeneficial effects are considerably less apparent and undesirableoff-notes can become increasingly apparent.

Interesting organoleptic effects, e.g. salt, alcohol or coolant boostingeffects, in edible compositions containing salt or alcohol or coolantcompounds can be achieved when compounds of the formula (I) are employedat levels of 1 to 100 ppb.

Interesting organoleptic effects, for example umami boosting effects, inedible compositions containing umami tastants can be achieved whencompounds of the formula (I) are employed at levels of 100 to 250 ppb.

Interesting organoleptic effects, in particular mouthfeel boostingeffects, in edible compositions can be achieved when compounds of theformula (I) are employed at levels of 250 to 500 ppb.

Interesting organoleptic effects, e.g. fat boosting effects, in ediblecompositions containing fats can be achieved when compounds of theformula (I) are employed at levels of 500 to 1000 ppb.

It is particularly advantageous to incorporate compounds of formula (I)into edible compositions that are formed under conditions of hightemperature, such as baking, frying or which are processed by heattreatments such as pasteurization or under UHT conditions. Under highpreparation or processing temperatures, volatile flavour ingredients maybe lost or degraded with the result that flavour intensity can bereduced and the essential and authentic flavour characteristics can bediminished. Such edible products include dairy products, snack foods,baked products, powdered soft drinks and similar dry mixes, and thelike, fats and condiments, mayonnaise, dressings, soups and bouillons,and beverages.

A particularly preferred class of edible composition according to thepresent invention are powdered soft drinks and similar dry mixapplications. Dry mix applications are known in the art and includedproducts in powder form that are intended to be reconstituted beforeconsumption. They include powdered soups, powdered cake mixes, powderedchocolate drinks, instant coffees, seasonings and fonds, and the like.

Dry powders formed by dispersive evaporation processes, such as spraydrying, represent a very convenient vehicle to deliver flavour oilquality flavours to edible compositions.

Unfortunately, flavour oils, and in particular citrus flavour oils canbe particularly sensitive to dispersive evaporation processes,especially processes carried out at high temperature. Flavour oils tendto evaporate or degrade to form products having unfavourable off-notes.Powdered flavour compositions, particularly those containing citrusoils, can be of poor quality and exhibit relatively short self-life, asa result.

Surprisingly, the incorporation of compounds of formula (I) or flavourcompositions containing same into powder compositions, results in powdercompositions that exhibit the impact and authenticity of the flavouroils used in their preparation, essentially maintaining flavour oilquality in a powdered flavour formulations.

Accordingly, the invention provides in another aspect a powder flavourcomposition comprising a compound according to formula (I) and at leastone additional flavour co-ingredient.

In another aspect of the invention there is provided a powder soft drinkcomposition or other dry mix composition comprising a compound accordingto formula (I).

In yet another aspect of the present invention there is provided apowder soft drink composition or other dry mix composition comprising apowder flavour composition comprising a compound of formula (I).

In yet another aspect of the present invention there is provided amethod of forming a powder flavour composition comprising the step ofincorporating into said composition a compound according to formula (I).

In a particular embodiment of the compound of formula (I) may be addedto the formed powder flavour composition, or it may be added to flavourcomposition before forming the powder.

Another particularly preferred class of edible composition according tothe present invention are snack foods. Snack foods are a category ofproduct well known to the skilled person in the food industry. Theseproducts are described above and include, without limitation, pretzels,corn chips, potato chips, puffed products, extruded products, tortillachips and the like. Still more particularly, the invention is concernedwith low fat snack food compositions. Low fat snack food compositionscontain less that 30% by weight fat, more particularly between 5 to 25%by weight of fat.

A problem with reducing fat in a snack food composition is the loss intaste and texture. Fats play an important role in the way that doughbehaves during processing and greatly affect the quality, flavor andtexture of ready-to-eat products. As the fat content in snack productsis reduced or replaced with other ingredients (e.g., non-digestible fat,protein, fiber, gums), adverse organoleptic effects (e.g., mouthcoating, drying, lack of crispness and lack of flavour) are increased.The adverse organoleptic effects result in products having reducedpalatability.

Considerable efforts have been expended in devising flavour compositionsto overcome the problems associated with low fat snack food products.Flavours may be applied to a snack food as topical coatings in the formof dry powders and/or as liquids (e.g., oil-based, water-based). Anotherapproach has been to add flavour to the dough.

Despite these various approaches which have been taken to improveconsumer appeal and palatability of snack foods, and particularly lowfat snack foods, there is still a need for improved low-fat snack foodshaving coatings applied thereto with the visual appeal, flavor, andtexture of full-fat snack foods.

Compounds according to formula (I) or flavour compositions containingsame can be incorporated into snack foods to impart an impactful flavourand a mouthfeel with a remarkable roundness and fullness. Furthermore,the taste and mouthfeel effects can be achieved even in low fat snackfoods.

Accordingly, the invention provides in another of its aspects a snackfood comprising a flavour composition as hereinabove described. In aparticular embodiment of the invention the snack food has a fat contentof about 40% or less by weight based on the total weight of the snackfood, more particularly about 30% or less, still more particularly 25%or less, more particularly still about 10% or less, still moreparticularly about 5% or less, still more particularly about 3% or less.

Examples of snack foods are described above and include productsprocessed by oven baking, extrusion or frying, and which are made frompotato and/or corn and/or various grains such as rice or wheat.

Another particularly preferred class of edible composition according tothe present invention is alcoholic beverages.

Applicant surprisingly found that compounds according to formula (I)incorporated into an alcoholic beverage had the effect of increasing thealcohol impact of the beverage.

Accordingly, the invention provides in another of its aspects analcoholic beverage comprising a compound according to formula (I).

In yet another aspect of the invention there is provided a method ofproducing a heightened alcoholic impression in an alcoholic beverage byincorporating into said beverage a compound according to formula (I).

Compounds of formula (I) may be incorporated into said alcoholicbeverage in amounts of 1 ppb to 1 ppm.

Another preferred class of edible compositions are products ingested inthe form of tablets, capsules, powders, multiparticulates and the like,which may include pharmaceuticals and nutraceuticals.

Certain groups of people have problems swallowing tablets or capsules,powders, multiparticulates and the like. This problem can beparticularly pronounced in certain consumer groups, such as children andthe very old or infirm. Applicant surprisingly found that compoundsaccording to the formula (I) when taken into the oral cavity produce apronounced salivating effect. Incorporating the compounds into thesedosage forms, particularly as part of a coating around said dosage formscan ease the swallowing process for consumers, in particular childrenand the old or infirm.

Accordingly, the invention provides in another of its aspects an orallyadministrable dosage form, in particular in the form of tabletscapsules, powders or multiparticulates comprising a compound accordingto the formula (I).

Another preferred class of edible composition is baked goods. Compoundsof the formula (I) may be incorporated topically or in-dough.Incorporated at levels of 1 ppb to 1 ppm, the compounds of formula (I)render baked products less dry and more succulent.

Other preferred class of edible compositions are caloric or non-caloricbeverages containing carbohydrate sweeteners, such as sucrose, highfructose corn syrup, fructose and glucose, or high intensity,non-nutritive sweeteners such as aspartame, acesulfame K, sucralose,cyclamate, sodium saccharin, neotame, rebaudioside A, and/or otherStevia-based sweeteners; as well as other optional ingredients such asjuices, organic acids such as citric acid, alcohol and functionalingredients.

Incorporated at levels of 1 ppb to 10 ppm, compounds of formula (I)impart to said beverages containing sweeteners at levels of less than 1%and up to about 20%, an upfront sweetness and mouthfeel that isreminiscent of sugar.

Other preferred edible compositions are savoury compositions, inparticular those that are soy-based or fish-based.

Incorporated at levels of 1 ppb to 10 ppm, in a soy-based composition(such as soy sauce) or a fish-based composition (such as fish sauce)containing 5 to 40% salt, the compositions are found to exhibit strongumami tastes that are long-lasting and rich.

Another preferred edible composition is a clouded beverage composition.

Certain beverages such as juices have relatively higher turbidity andthus have an opaque appearance. Often, it is desired that the beveragehave a relatively high turbidity. This might be desirable to provide amore natural appearance to beverages with low juice content, or it mightbe for reasons related to masking sedimentation or “ringing” (whereflavour or colour oils rise to the surface of a container duringstorage). Clouded beverages are usually formed by means of a cloudingagent. Clouding agents are usually supplied in the form of emulsions, orthe clouding agent may be part of a powdered beverage that uponreconstitution will formed an emulsion providing a permanent cloud tothe beverage.

Compounds of the formula (I), in addition to their remarkableorganoleptic properties, can lend stability to clouding agents and tobeverage compositions containing same.

Accordingly, the invention provides in another of its aspects acomposition comprising a beverage clouding composition and a compound offormula (I).

In a particular embodiment of the invention, a flavour composition asherein defined may be provided in the form of an emulsion. This emulsioncomposition may be particularly useful in clouded beverage applications,in particular, in which it is intended to employ a clouding agent.

In yet another aspect of the invention there is provided a cloudedbeverage composition comprising a clouding agent and a compound of theformula (I).

Other preferred edible compositions are those compositions that areformed by a process of ripening.

In food processing, it frequently occurs that a food needs to remain fora prolonged period of time and under well-defined conditions to obtainthe food with the requisite and recognised quality. A commonly used termfor this process is ripening. Ripening is well known in the processingof certain types of cheese, meat, soy-sauce and wine, as well as beersausage, sauerkraut, tempeh and tofu. There are also specific steps thatare carried out for specific reasons (such as water-removal, or off-noteremoval) that have beneficial effects on the food products. Examples ofthis are the conching of chocolate and the drying of noodles, vegetablesand fruits. The transformations that improve the quality of the food areinduced by chemical conversions, enzymatically catalysed conversions orfermentative transformations. All of these conversions are slow andtherefore expensive; they are also not fully predictable orcontrollable.

The compounds of formula (I), having regard to their remarkable propertyof adding to the authentic taste characteristics of the ediblecompositions in which they are incorporated, may be added to an edibleproduct during its ripening process in order to reduce storage timewithout adversely influencing the taste quality of the ripened product.

Accordingly, in another aspect of the invention there is provided amethod of ripening a product selected from the group consisting ofcheese, meat, soy-sauce and wine, beer, sausage, sauerkraut, tempeh andtofu, comprising the step of ripening the product in the presence of acompound according to the formula (I).

In another aspect of the invention there is provided a method ofconching chocolate, said method comprising the step of adding to thechocolate a compound according to the formula (I), or a flavourcomposition containing same.

There now follows a series of non-limiting examples that serve toillustrate the invention.

SYNTHESIS EXAMPLES 1. General Structure

R¹=is a straight chain hydrocarbon group having 9 to 21 carbon atoms andcontaining zero to three double bonds

or

R¹ is a [(1E)-2,6-dimethylhepta-1,5-dien-1-yl]-group.

Several compounds belonging to that general formula have beensynthesised according to one of the 2 procedure described below.

2. Synthesis

2.1 Route A: (DCC Method)

In a 250 mL round-bottomed flask was mixed fatty acid (3.93 mmol) with1-hydroxypyrrolidine-2,5-dione (0.498 g, 4.32 mmol) in dioxane (50 ml)to give a colorless solution. The solution was cooled to 10° C. and DCC(0.892 g, 4.32 mmol) was added while stirring. Stirring was continuedfor three hours at room temperature. The formed solids were filtered(dicyclohexylurea) and the filtrate was added to a solution of aminoacid (6.48 mmol) in a 2% solution of sodiumbicarbonate (0.363 g, 4.32mmol) in water. The reaction mixture was stirred for 4 hours at 50° C.Dioxane was evaporated and the aqueous residue was further diluted withwater, acidified with a diluted hydrochloric acid solution and extractedwith ethylacetate. Organic layers were combined, washed with brine,dried and evaporated to yield 1.3 g of a white solid. Product waspurified by flash column chromatography, eluent DCM/methanol.

1 g of 85-90% pure product could be obtained.

2.2 Route B (DCC Method with Protection Group)

Step 1:

To a solution of an O-methylated amino acid (16.51 mmol) in DCM (100 ml)was added triethylamine (1.519 g, 15.01 mmol) at minus 15° C. A fattyacid (0.01 mmol) was added while stirring. A solution of DCC (15.01mmol) in 10 mL of DCM was added dropwise at 0° C. The reaction mixturewas stirred at 0° C. for 1 hour and stirring was continued at roomtemperature for 3 hours. The dicyclohexylurea was removed by filtrationfrom the reaction mixture. Filtrate was washed with a saturatedsodiumbicarbonate solution, diluted hydrochloric acid solution andwater. Organic layer was separated, dried and evaporated to yield 3 g ofan oil. This oil was purified by flash column chromatography, eluentDCM/methanol The intermediate ester compound could be isolated in apurity of 95%.

Step 2:

The O-methylated N-acyl-amino-acid (4.91 mmol) was dissolved in amixture of Ethanol (8.00 ml) and water (8 ml). To this mixture was addeda 32% solution of sodiumhydroxide (2.453 g, 19.63 mmol) and mixture wasstirred at room temperature for three hours. Mixture stand over for 14hours.

After 14 hours the mixture was acidified with a concentratedhydrochloric acid solution (1.612 ml, 19.63 mmol), diluted with waterand extracted with mtbe. Organic layer was separated, dried andevaporated. 1.3 g of a half solid yellow residue was obtained. NMRconfirmed the structure of the title compound, purity 95%

2.3 Route C (Acid Chloride)

An amino acid (20 mmol) was dissolved in a solution of sodiumhydroxide(54.5 mmol) in water (40 ml).

Tetrahydrofuran (60 ml) was added. Fatty acid chloride (18.18 mmol) wasadded dropwise at room temperature. Stirring was continued for 2 hours.Mixture was diluted with water, acidified with a 37% solution ofhydrochloric acid (2.99 ml, 36.4 mmol) and extracted with ethylacetate.

Organic layers were combined, dried and evaporated.

The residue contains about 20% free fatty acid according NMR. The solidswere stirred with heptane for 30 minutes, filtered and dried. Thisresulted in 2.4 g of the title compound as a creamy colored solid.(purity 95%).

2.4 All Synthesized Compounds

TABLE 1 List of synthesized compounds Amino Carboxylic Structure acidacid Structure Route 1 Proline C10:2

A 2 Proline C16:0

C 3 Proline C16:0

C 4 Proline C18:2

A

3. NMR Data (Example)

3.1 Structure 4 Proline-C18:2

¹H NMR (600 MHz, CHLOROFORM-d)

ppm 0.78-0.85 (m, 3H, H—C(18)) 1.18-1.33 (m, 14H, H—C(4, 5, 6, 7, 15,16, 17) 1.54-1.65 (m, 2H, H—C(3)) 1.84-1.92 (m, 1H, H_C(22)) 1.92-2.03(m, 6H, H_C(8, 14, 23)) 2.26-2.32 (m, 2H, H—C(2)) 2.44 (ddd, J=12.29,6.10, 2.92 Hz, 1H, H—C(22)) 2.70 (t, J=6.70 Hz, 2H, H—C(11)) 3.39 (td,J=9.62, 6.87 Hz, 1H, H—C(24)) 3.47-3.53 (m, 1H, H—C(24)) 4.53 (dd,J=8.08, 1.89 Hz, 1H, H—C(21)) 5.16-5.36 (m, 4H, H—C(9, 10, 12, 13)

¹³C NMR (150 MHz, CHLOROFORM-d)

ppm 14.07 (C(18)) 22.57 (C(17)) 24.48 (C(3)) 24.79 C(23)) 25.62 (C11))27.05 (C(22)) 27.17 (C(8)) 27.19 (C(14)) 29.10 C(6)) 29.27 (C(4, 15))29.34 (C(5)) 29.60 C(7)) 31.51 C((16)) 34.45 C(2)) 47.98 C(24)) 60.25(C(21)) 128.07 (C(12)) 128.07 (C(10)) 130.00 (C(9)) 130.24 C(13)) 171.87(C(1)) 175.87 (C20))

Application Examples

Testing Proline Derivatives

Samples were evaluated by expert tasters. Tasters were asked to describethe samples focusing on authentic taste, mouthfeel, fullness,salty-ness, salivation, umami, sweetness, juiciness, richness, longlastingness and fattiness.

Comparison in a Mango Juice Drink

Base is water, 8% sucrose, 0.1% citric acid, 1% clear mango juice,proprietary mango flavour @ 0.05%

Base: Fruity mango

Base plus C16:0-pro at 1 ppm overripe, orange like, long lasting aftertaste

Base plus C18:1-pro at 1 ppm sweet, orange albedo

Test in Orange Beverage

Base is water, 7% sugar, 0.1% citric acid, proprietary orange flavour @0.06%.

Base: orange, fruity, slightly candy

Base plus C18:2-pro at 1 ppm: very juicy, authentic orange

Test in Lemon Beverage

Basis water, 7% sucrose, 0.15% citric acid, proprietary lemon flavor

Base: floral, citral, lemon

Base plus C18:2-pro at 1 ppm: very juicy, more citral like, veryauthentic.

Test in Bouillion

Base is Maggi beef bouillon 1 tablet in 500 ml of hot water

Base: salty, umami, powdery

Base plus C16:0-pro at 1 ppm: more salty, full, darker, more meat-like

Base plus C18:1-pro at 1 ppm: full, more umami, long lasting

The invention claimed is:
 1. A flavour composition comprising a compoundselected from the group consisting of: N-geranoyl-Pro,N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro, and,N-linolenoyl-Pro, wherein, the compound accentuates the existing flavouror existing mouth feel characteristics of edible foodstuff productsfurther comprising at least one flavour co-ingredient, or of beverageproducts further comprising at least one flavour co-ingredient, when thesaid compound is incorporated in an amount of 1 ppb-10 ppm within theedible foodstuff product or beverage product.
 2. A stock solutioncomprising 0.01 to 1% by weight of a compound of claim 1, wherein thecompound accentuates the existing flavour or existing mouth feelcharacteristics of edible foodstuff products further comprising at leastone flavour co-ingredient, or of beverage products further comprising atleast one flavour co-ingredient when the compound is incorporatedtherein in an amount of 1 ppb-10 ppm within the edible foodstuff productor beverage product.
 3. A stock solution according to claim 2 furthercomprising a solvent selected from the group consisting of: ethanol,triacetine, glycerol and miglyol or mixtures thereof.
 4. A method ofaccentuating the flavour or mouthfeel characteristics of an ediblefoodstuff composition, the method comprising the step of incorporatingthe flavour composition of claim 1 in the edible composition such that acompound is present in a concentration of 1 ppb-10 ppm within the ediblefoodstuff composition.
 5. The flavour composition according to claim 1further comprising at least one flavour co-ingredient.
 6. The flavourcomposition according to claim 1 further comprising an ingredientselected from the group consisting of: sugars, fats, salt, MSG, calciumions, phosphate ions, organic acids, proteins, purines and mixturesthereof.
 7. The flavour composition according to claim 1 furthercomprising a carrier material and an adjuvant.
 8. The flavourcomposition according to claim 7 wherein the adjuvant is ananti-oxidant.
 9. The flavour composition according to claim 1 in theform of an emulsion.
 10. The flavour composition according to claim 1 inthe form of a powder.
 11. An edible foodstuff product or a beverageproduct comprising a flavour composition according to claim 1,comprising 1 ppb-10 ppm of a compound selected from the group consistingof N-geranoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro,N-linoleoyl-Pro and N-linolenoyl-Pro.
 12. A caloric or non-caloricbeverage product comprising an edible composition according to claim 11containing at least one carbohydrate sweetener selected from: sucrose,high fructose corn syrup, fructose and glucose, or at least one highintensity, non-nutritive sweetener selected from: aspartame, acesulfameK, sucralose, cyclamate, sodium saccharin, neotame, rebaudioside A,and/or Stevia-based sweeteners.
 13. A soy-based edible compositioncomprising an edible foodstuff product according to claim
 11. 14. Anedible foodstuff product or a beverage product comprising a compoundselected from the group consisting of N-geranoyl-Pro,N-palmiteneoyl-Pro, N-stearoyl-Pro, N-oleoyl-Pro, N-linoleoyl-Pro andN-linolenoyl-Pro as defined in claim 1, and a flavour co-ingredient. 15.An edible foodstuff product or a beverage product according to claim 14wherein the compound imparts enhanced fat perception.
 16. An ediblefoodstuff product or a beverage product according to claim 14 whereinthe compound imparts enhanced umami taste.
 17. An edible foodstuffproduct or a beverage product according to claim 14 wherein the compoundimparts enhanced salt taste.
 18. An edible foodstuff product or abeverage product according to claim 14 wherein the compound impartsenhanced fruit profiles.
 19. An edible foodstuff product or a beverageproduct according to claim 14 wherein the compound imparts enhancedsavoury character.
 20. An edible foodstuff product or a beverage productaccording to claim 14 wherein the compound imparts improved flavourperformance.
 21. An edible foodstuff product according to claim 14wherein the compound imparts enhanced salivation.